Institute for Chemical Research , Kyoto University , Uji , Kyoto 611-0011 , Japan.
Langmuir. 2018 Aug 14;34(32):9532-9539. doi: 10.1021/acs.langmuir.8b02073. Epub 2018 Aug 2.
The development of new magnetic materials for applications such as magnetic-driven drug delivery, next-generation display materials, and magnetic resonance imaging is an important objective. To that end, we synthesized monodispersed, magnetically responsive particles grafted with well-defined polymer brushes and investigated the formation of their ordered arrays in organic solvents in response to a magnetic field. To achieve this, we prepared monodispersed magnetic nanoparticle clusters (MNCs) composed of large numbers of superparamagnetic ferrite ZnFeO nanoparticles. The MNCs were subsequently coated with thin silica layers through the hydrolysis of tetraethoxysilane. The colloidal particles were surface-modified with initiating groups for atom transfer radical polymerization (ATRP) using a triethoxysilane derivative with an ATRP initiation site. To demonstrate the ability of the synthesized particles to produce well-defined polymer brushes on their surfaces, the ATRP-initiator-functionalized silica-coated MNCs were subjected to surface-initiated ATRP with methyl methacrylate. This polymerization proceeded in a living fashion to produce graft polymers with targeted molar masses and narrow molar mass distributions. The average graft density was determined to be 0.65 chains/nm, which confirms the formation of concentrated polymer brushes on the MNCs. The hybrid particles were analyzed by dynamic light scattering and transmission electron microscopy techniques, which revealed excellent uniformity and solvent dispersibility. A suspension of the polymer-brush-decorated MNCs in acetone quickly developed intense structural color in response to approaching a magnet that depended on the strength of the magnetic field.
开发用于磁驱动药物输送、下一代显示材料和磁共振成像等应用的新型磁性材料是一个重要目标。为此,我们合成了单分散的、对磁响应的颗粒,接枝上具有明确聚合物刷的聚合物,并研究了它们在有机溶剂中形成有序排列的情况,这种有序排列是对磁场的响应。为了实现这一目标,我们制备了由大量超顺磁铁酸盐 ZnFeO 纳米颗粒组成的单分散磁性纳米颗粒簇(MNC)。随后,通过四乙氧基硅烷的水解在 MNC 上包覆了薄的二氧化硅层。通过使用具有 ATRP 引发点的三乙氧基硅烷衍生物,将引发基团接枝到胶体颗粒的表面,从而对其进行原子转移自由基聚合(ATRP)表面改性。为了证明合成颗粒在其表面产生具有明确聚合物刷的能力,用甲基丙烯酸甲酯对 ATRP-引发剂功能化的二氧化硅包覆的 MNC 进行表面引发 ATRP。聚合以活的方式进行,从而产生具有目标摩尔质量和较窄摩尔质量分布的接枝聚合物。平均接枝密度被确定为 0.65 条/纳米,这证实了在 MNC 上形成了浓缩聚合物刷。通过动态光散射和透射电子显微镜技术对杂化颗粒进行了分析,结果表明其具有优异的均一性和溶剂分散性。聚合物刷修饰的 MNC 在丙酮中的悬浮液在接近磁场时会迅速产生强烈的结构色,其颜色的强度取决于磁场的强度。